EP0578983A1 - Procédé de préparation d'hydrides d'étain trialkylique - Google Patents

Procédé de préparation d'hydrides d'étain trialkylique Download PDF

Info

Publication number
EP0578983A1
EP0578983A1 EP93109590A EP93109590A EP0578983A1 EP 0578983 A1 EP0578983 A1 EP 0578983A1 EP 93109590 A EP93109590 A EP 93109590A EP 93109590 A EP93109590 A EP 93109590A EP 0578983 A1 EP0578983 A1 EP 0578983A1
Authority
EP
European Patent Office
Prior art keywords
nabh4
trialkyltin
process according
bis
hydrides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93109590A
Other languages
German (de)
English (en)
Other versions
EP0578983B1 (fr
Inventor
Ralf-Jürgen Dr. Dipl.-Ing. Becker
Ulrich Dr. Dipl.-Chem. Stewen
Udo Chem. Weinberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemtura Organometallics GmbH
Original Assignee
Witco GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Witco GmbH filed Critical Witco GmbH
Publication of EP0578983A1 publication Critical patent/EP0578983A1/fr
Application granted granted Critical
Publication of EP0578983B1 publication Critical patent/EP0578983B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen

Definitions

  • the present invention relates to an improved process for the preparation of trialkyltin hydrides of the general formula R1R2R3SnH, which, due to the process control, have excellent storage stability.
  • Organotin hydrides are valuable and extremely versatile reagents for organic synthesis. This is demonstrated by a large number of publications. Detailed information can be found in some reviews, e.g. B. W. P. Neumann, Synthesis 1987, 665; B. Giese, Radicals in Organic Synthesis: Formation of Carbon Bonds, Pergamon Press, Oxford 1986; M. Pereyre, J.P. Quintard and A. Rahm: Tin in Organic Synthesis, Butterworth, London 1987; D.P. Curran, Synthesis 1988, 417, 489; I. Omar, Organotin Chemistry, Elsevier, Amsterdam 1989; P.G. Harrison, Chemistry on Tin, Blackie, Glasgow and London 1989.
  • the instability is caused in particular by traces of impurities which remain in the product as a result of the production and act directly as decomposition catalysts. So cause traces of Lewis acids, such as. B. aluminum halides, boron halides, organoaluminium and organotin halides, the immediate decomposition.
  • US-A-4 282 166 describes a process for the preparation of trialkyltin hydrides from trialkyltin chloride and sodium bis (2-alkoxyethoxy) aluminum dihydride.
  • CA 90: 204.205 p describes the reduction of trialkyltin chloride with NaBH4 in ether-water mixtures with yields of 65 - 80%.
  • alkyltin oxides and chlorides can be converted to tin hydrides (K. Hayashi et al, J. Organomet. Chem., 10 (1), 81-94; JP 43.010.134 (CA 69: 106.880 b); JP 43.010.133 (CA 69: 106.879 h); JP 43.012.132 (CA 70: 37 922 y); DE 3 119 643).
  • LiAIH4 provides trialkyltin hydrides in yields between 66 - a maximum of 89% (HJ Albert, TN Mitchell, WP Neumann, Methodicum Chimicum, H. Zimmer, Ed., Vol. 7, Part A, Academic Press, New York, 1977, 361-2).
  • Trialkyltin chlorides can be reacted in good yields with NaBH,, the reaction and the workup are complex and cumbersome (J. Organomet. Chem., 9 (2), 379-82 (1967).
  • Patent HU-A-41.412 describes a process for the preparation of tri-n-butyltin hydride from bis- [tri-n-butyltin] oxide, which is characterized in that bis- [tri-n-butyltin] oxide in an aliphatic alcohol dissolves and can react at a temperature of 10 - 30 ° C with an alcoholic and / or aqueous NaBH4 solution for 10 - 60 min. After complex cleaning steps, tri-n-butyltin hydride is isolated in yields between 64-84%.
  • the process according to the invention allows, starting from inexpensive, readily available starting compounds, the production of high-purity qrganotin hydrides in quantitative yield, which, apparently due to the extraction and neutralization effect, are free of decomposition initiators or catalysts.
  • an inert solvent is advantageously chosen which does not react either with organotin hydrides or with NaBH4.
  • Suitable solvents are diethyl ether, dioxane, acetonitrile, hydrocarbons, preferably tetrahydrofuran.
  • the starting compounds are preferably used in a stoichiometric or approximately stoichiometric ratio in the range from 0.5 to 1.5 mol NaBH4 to 1 mol bis- [trialkyltin] oxide.
  • a stabilized aqueous NaBH4 solution is advantageously used for safe handling, for which bases such as sodium hydroxide are particularly suitable.
  • hydrogen-acidic compounds such as thiosalicylic acid, lactic acid, lauryl mercaptan, preferably thioglycolic acid, are preferably added.
  • antioxidants are also advantageous.
  • Typical radical scavengers can be used for this, such as. B. BHT (2,6-di-tert-butyl-4-methylphenol), 3-tert-butyl-4-hydroxyanisole, pyrogallol and / or typical metal ion deactivators, such as. B. triphenylphosphine, 4,4-thiobis (2-tert-butyl-5-methylphenol), ethylenediamine-N, N, N ', N'-tetra-2-propanol, N', N'-diphenyl-1,4-phenylenediamine.
  • reaction of bis- [trialkyltin] oxides with an aqueous, stabilized NaBH4 solution can be easily controlled by controlled metering in of the reducing agent.
  • the reverse reaction, i.e. Presentation of the NaBH4 solution is possible without loss of yield.
  • the reaction can be carried out either continuously or batchwise.
  • the upper organic phase contains the trialkyltin hydride and, if the metering has not ended, the unreacted bis- [trialkyltin] oxide.
  • the lower aqueous phase contains the reducing agent NaBH4 and its oxidation products.
  • the lower aqueous phase is separated and can, for. B. be used again after enrichment with NaBH4.
  • the solvent is distilled off from the upper organic phase, which contains the organotin hydride. There is no additional cleaning of the product.
  • trialkyltin hydrides can be prepared in highly pure form and in almost quantitative yield by the extraction and neutralization effect of the basic aqueous phase.
  • the trialkyltin hydrides are free of decomposition initiators or catalysts without additional purification and therefore have excellent storage stability.
  • Tributyltin hydride is isolated in approximately quantitative yield from the reaction analogous to Example 1, but with the additional use of 3% BHT.
  • reaction conditions are chosen analogously to Example 5. Lactic acid is used as an accelerator instead of thiosalicylic acid.
  • reaction conditions are chosen analogously to Example 5. Instead of thiosalicylic acid, lauryl mercaptan is used as an accelerator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Steroid Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP93109590A 1992-07-17 1993-06-16 Procédé de préparation d'hydrides d'étain trialkylique Expired - Lifetime EP0578983B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4223615 1992-07-17
DE4223615A DE4223615A1 (de) 1992-07-17 1992-07-17 Verfahren zur Herstellung von Trialkylzinnhydriden

Publications (2)

Publication Number Publication Date
EP0578983A1 true EP0578983A1 (fr) 1994-01-19
EP0578983B1 EP0578983B1 (fr) 1998-02-18

Family

ID=6463494

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93109590A Expired - Lifetime EP0578983B1 (fr) 1992-07-17 1993-06-16 Procédé de préparation d'hydrides d'étain trialkylique

Country Status (10)

Country Link
US (1) US5288886A (fr)
EP (1) EP0578983B1 (fr)
JP (1) JP3338130B2 (fr)
AT (1) ATE163292T1 (fr)
AU (1) AU659005B2 (fr)
CA (1) CA2098213C (fr)
DE (2) DE4223615A1 (fr)
DK (1) DK0578983T3 (fr)
ES (1) ES2114970T3 (fr)
MX (1) MX9304278A (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877336A (en) * 1996-12-31 1999-03-02 Bridgestone Corporation Synthesis of tributyltin lithium
WO2007092601A2 (fr) * 2006-02-08 2007-08-16 Los Alamos National Security, Llc Synthèse de boranes économe en énergie

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381395A (fr) * 1962-10-19 1964-12-14 Studiengesellschaft Kohle Mbh Procédé pour la stabilisation d'hydrures organo-stanniques

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1167345B (de) * 1960-11-08 1964-04-09 Studiengesellschaft Kohle Mbh Verfahren zur Stabilisierung von Organozinnhydriden
DE1468709A1 (de) * 1960-11-08 1969-05-08 Studiengesellschaft Kohle Mbh Verfahren zur Stabilisierung von Organozinnhydriden
US3401183A (en) * 1965-12-23 1968-09-10 Gen Electric Method for preparing organo germanium, tin and silicon hydrides
US3439008A (en) * 1966-03-31 1969-04-15 Gen Electric Method for making organometallic hydrides
US4282166A (en) * 1980-04-11 1981-08-04 Argus Chemical Corporation Preparation of lower trialkyltin hydride from trialkyltin chloride
DE3119643A1 (de) * 1981-05-16 1982-12-02 Paul Rauschert Gmbh & Co Kg, 8644 Pressig Zinnorganische verbindungen, verfahren zu deren herstellung und deren verwendung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381395A (fr) * 1962-10-19 1964-12-14 Studiengesellschaft Kohle Mbh Procédé pour la stabilisation d'hydrures organo-stanniques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY & INDUSTRY Bd. 23, 1988, Seite 764 J. SZAMMER ET AL *
DATABASE WPIL Week 8721, Derwent Publications Ltd., London, GB; AN 87-145433 *
SYNTHESIS Bd. 9, 1983, Seite 722 A.B. CHOPA ET AL *

Also Published As

Publication number Publication date
AU3981893A (en) 1994-01-20
JP3338130B2 (ja) 2002-10-28
EP0578983B1 (fr) 1998-02-18
JPH06179687A (ja) 1994-06-28
CA2098213C (fr) 1997-12-16
MX9304278A (es) 1994-08-31
CA2098213A1 (fr) 1994-01-18
DE59308155D1 (de) 1998-03-26
ES2114970T3 (es) 1998-06-16
AU659005B2 (en) 1995-05-04
DK0578983T3 (da) 1998-09-28
ATE163292T1 (de) 1998-03-15
US5288886A (en) 1994-02-22
DE4223615A1 (de) 1994-01-20

Similar Documents

Publication Publication Date Title
EP0718235B1 (fr) Méthode de préparation d'hydrure d'aluminium exempt d'éther et d'halogénure
DE2540210C3 (de) Verfahren zur Herstellung von Organozinntrihalogeniden
DE69533739T2 (de) Herstellung von Triorganozinn-Lithium-Zusammensetzungen und deren Verwendung als Initiatoren
DE69219211T2 (de) Hydrochlorierung katalytisches System und Verfahren zur Herstellung von Vinylchlorid aus Acetylen und Chlorwasserstoff, in Gegenwart dieses katalytischen Systems
EP0592779B1 (fr) Procédé pour la préparation de distannanes
EP0578983B1 (fr) Procédé de préparation d'hydrides d'étain trialkylique
DE69310363T2 (de) Verfahren zur herstellung von trialkylverbindungen von metallen der gruppe 3a
DE2226774C3 (de) Verfahren zur Herstellung von Distannanen der Formel R↓3↓Sn-Sn R↓3↓
DE4424222C1 (de) Gelöstes Methyllithium enthaltendes Synthesemittel sowie Verfahren zu deren Herstellung
DE3723713C2 (fr)
DE2720911C3 (de) Verfahren zur Herstellung von n-Hexyl-Carboran
EP1295887B1 (fr) Préparation de composés aryllithium purs
DE2945348C2 (de) Verfahren zur Herstellung von Erdalkalialkoxyalanaten
DE2101207A1 (de) Cyclische Stickstoff enthaltende Organosihciumverbindungen
DE1280867B (de) Verfahren zur Deuterierung von organischen Verbindungen
DE1206913B (de) Verfahren zur Herstellung von 2, 4, 6-Tri-secundaer-alkyl-1, 3-dioxa-5-phosphacyclohexanen
DE2460288C3 (de) Verfahren zur Herstellung von Tricyclohexylzinnchlorid oder -bromid
WO2001077117A1 (fr) Procede de production de boranates monohydrido de metal alcalin et d'aluminates monohydrido de metal alcalin
DE3000490C2 (de) Verfahren zur Herstellung von Erdalkali-Alkoxyalanaten
DE808837C (de) Verfahren zur Herstellung von Saeurechloriden der Thio- und Dithiodiglykolsaeuren
DE2427617A1 (de) Verfahren zur herstellung von trineophylzinnhalogeniden
DE2456600C3 (de) Verfahren zur Herstellung von Poly-N-alkyllmlnoalanen
CH433292A (de) Verfahren zur Herstellung von Aminophosphinen
DE1069627B (de) Verfahren zur Zerlegung von Origanomagnesiumharogenid-Komplexverbindungen
DE1178851B (de) Verfahren zur Herstellung asymmetrischer Borazole

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19940705

17Q First examination report despatched

Effective date: 19970416

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 163292

Country of ref document: AT

Date of ref document: 19980315

Kind code of ref document: T

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59308155

Country of ref document: DE

Date of ref document: 19980326

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980519

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2114970

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: WITCO GMBH TRANSFER- CK WITKO GMBH * CK WITKO GMBH TRANSFER- CROMPTON GMBH

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: CROMPTON GMBH;CK WITCO GMBH

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20040603

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20040621

Year of fee payment: 12

Ref country code: DK

Payment date: 20040621

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050630

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: CHEMTURA ORGANOMETALLICS GMBH

Free format text: CROMPTON GMBH#ERNST-SCHERING-STRASSE 14#59192 BERGKAMEN (DE) -TRANSFER TO- CHEMTURA ORGANOMETALLICS GMBH#ERNST-SCHERING-STRASSE 14#59192 BERGKAMEN (DE)

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: SCHMAUDER & PARTNER AG PATENTANWALTSBUERO

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: CHEMTURA ORGANOMETALLICS GMBH

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: SCHMAUDER & PARTNER AG PATENT- UND MARKENANWAELTE VSP;ZWAENGIWEG 7;8038 ZUERICH (CH)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20120620

Year of fee payment: 20

Ref country code: CH

Payment date: 20120427

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120525

Year of fee payment: 20

Ref country code: FR

Payment date: 20120614

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120619

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20120618

Year of fee payment: 20

Ref country code: DE

Payment date: 20120629

Year of fee payment: 20

Ref country code: BE

Payment date: 20120710

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59308155

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20130616

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BE20 Be: patent expired

Owner name: *CHEMTURA ORGANOMETALLICS G.M.B.H.

Effective date: 20130616

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20130615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130618

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130615

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130617